US5294247A - Adsorption process to recover hydrogen from low pressure feeds - Google Patents

Adsorption process to recover hydrogen from low pressure feeds Download PDF

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US5294247A
US5294247A US08/023,766 US2376693A US5294247A US 5294247 A US5294247 A US 5294247A US 2376693 A US2376693 A US 2376693A US 5294247 A US5294247 A US 5294247A
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bed
adsorption
adsorbable component
strongly adsorbable
hydrogen
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Eric W. Scharpf
Ravi Kumar
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Air Products and Chemicals Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • B01D53/0476—Vacuum pressure swing adsorption
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/102—Nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
    • B01D2259/40077—Direction of flow
    • B01D2259/40079—Co-current
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
    • B01D2259/40077—Direction of flow
    • B01D2259/40081—Counter-current
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/403—Further details for adsorption processes and devices using three beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/406—Further details for adsorption processes and devices using more than four beds
    • B01D2259/4062—Further details for adsorption processes and devices using more than four beds using six beds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/047—Composition of the impurity the impurity being carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/048—Composition of the impurity the impurity being an organic compound
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the present invention is directed to vacuum swing adsorptive processes for recovering hydrogen at high recoveries and high purities as an unadsorbed product from a feed gas at relatively low pressure and low hydrogen content, typically from refinery off gases.
  • U.K. Patent 2,154,465 discloses a vacuum swing adsorption process for recovering hydrogen in waste gas obtained in petrochemical plants.
  • the vacuum swing adsorption process described is conducted through a series of stages, including adsorption, simultaneous cocurrent depressurization to provide pressure equalization gas while countercurrently venting, providing purge to an evacuated bed, evacuation, purge under vacuum, product repressurization, and pressure equalization.
  • the patented process has discontinuous feed, while the dual end step provides equalization gas and rejects waste.
  • the patent also uses product repressurization before a final bed-to-bed equalization. The result of this process is that with a feed of 52% hydrogen, 42% nitrogen, 5% carbon monoxide and 1% carbon dioxide, the resulting hydrogen product is only 75% pure at a recovery of only 76%.
  • U.K. Patent 2,155,805 discloses a vacuum swing adsorption process for recovering hydrogen from flue gases from petrochemical plants, reduction furnaces and annealing furnaces.
  • This patent uses a similar cycle sequence to the above U.K. patent, but includes a feed gas and product gas repressurization step.
  • the patent describes a cocurrent depressurization to provide pressure equalization gas while simultaneously countercurrently venting the appropriate adsorption bed.
  • U.S. Pat. No. 4,981,499 describes a hydrogen pressure swing adsorption process in which cocurrent depressurization of the bed is made to a separate reservoir which supplies purge gas for other beds.
  • the cocurrent depressurization is conducted while performing a countercurrent vent of the former bed.
  • purging of a bed supplied with gas from the separate reservoir is not conducted at the same time as the cocurrent depressurization and countercurrent vent.
  • the present invention is a process for selectively separating at least one more strongly adsorbable component(s) from a less strongly adsorbable component of a feed gas mixture in a plurality of adsorption beds containing an adsorbent selective for the more strongly adsorbable component(s), comprising the steps of:
  • step (d) countercurrently purging the first bed with cocurrently depressurizing gas mixture from another bed of the plurality of adsorption beds undergoing step (b) to remove additional more strongly adsorbable component(s) from the first bed under the influence of a vacuum;
  • each bed is repressurized with feed gas mixture.
  • each bed is repressurized with less strongly adsorbable component.
  • each bed is repressurized with feed gas mixture and with said less strongly adsorbable component.
  • the first bed is cocurrently depressurized to pressure equalize with another bed at a lower pressure.
  • the first bed is simultaneously countercurrently depressurized to pressure equalize with another bed at lower pressure.
  • the first bed is at least partially repressurized by pressure equalization with another bed.
  • the first bed is cocurrently depressurized to supply pressure equalization gas for another bed.
  • step (a) adsorption less strongly adsorbable component is produced for a product and for repressurizing another bed. More preferably during step (a) adsorption, less strongly adsorbable component is produced for a product during a portion of the step (a) adsorption and less strongly adsorbable component is produced for a product and for repressurizing another bed simultaneously in another portion of the step (a) adsorption.
  • the feed gas mixture is a hydrogen-containing gas mixture
  • said more strongly adsorbable component(s) is selected from the group consisting of nitrogen, methane, carbon monoxide, carbon dioxide and mixtures thereof and said less strongly adsorbable component is hydrogen.
  • multiple beds are performing step (a) adsorption at a given time during the process.
  • multiple beds are performing step (c) evacuation at a given time during the process.
  • the present invention is a process for selectively separating at least one more strongly adsorbable component selected from the group consisting of nitrogen, methane, carbon monoxide, carbon dioxide and mixtures thereof from hydrogen in a hydrogen-containing feed gas mixture in a plurality of adsorption beds containing an adsorbent selective for the more strongly adsorbable component(s), comprising the steps of:
  • step (d) countercurrently purging the first bed with cocurrently depressurizing gas from another bed of the plurality of adsorption beds undergoing step (b) to remove additional more strongly adsorbable component(s) from the first bed under the influence of a vacuum;
  • the hydrogen-containing feed gas mixture contains less than 60% hydrogen.
  • the hydrogen-containing feed gas mixture is at a pressure less than 125 psig.
  • the hydrogen-containing feed gas mixture contains more than 1% carbon monoxide or carbon dioxide.
  • the adsorbent is selected from the group consisting of 13X-zeolite, 5A-zeolite, CaA-zeolite, activated carbon and mixtures thereof.
  • the adsorbent is layered in the plurality of adsorbent beds with a layer of activated carbon near a feed end of each bed, a layer of 13X-zeolite, a layer of 5A-zeolite and a layer of CaA-zeolite.
  • the process has a recovery of at least 80% of the hydrogen in the feed gas mixture.
  • the hydrogen recovered from the process has a purity of at least 950%.
  • the hydrogen-containing feed gas mixture is a refinery off gas.
  • the present invention is a process for selectively separating at least one more strongly adsorbable component(s) selected from the group consisting of nitrogen, methane, carbon monoxide, carbon dioxide and mixtures thereof from hydrogen in a hydrogen-containing feed gas mixture in six parallel connected adsorption beds containing an adsorbent(s) selective for the more strongly adsorbable component(s), comprising the steps of:
  • step (e) countercurrently purging the first bed with cocurrently depressurizing gas from another bed of the plurality of adsorption beds undergoing step (c) to remove additional more strongly adsorbable component(s) from the first bed under the influence of a vacuum;
  • step (g) repressurization is performed with product hydrogen and hydrogen-containing feed gas mixture.
  • step (b) pressure equalization is performed between the two beds by connecting their respective outlets and their respective inlets.
  • each bed has an idle period between step (f) pressure equalization and step (g) repressurization.
  • FIG. 1 is a series of schematic illustrations of an adsorption bed as it undergoes each step of the first embodiment of the present invention described in Table 1.
  • FIG. 2 is a series of schematic illustrations of an adsorption bed as it undergoes each step of the second embodiment of the present invention described in Table 2.
  • FIG. 3 is a series of schematic illustrations of an adsorption bed as it undergoes each step of the third embodiment of the present invention described in Table 3.
  • FIG. 4 is a series of schematic illustrations of an adsorption bed as it undergoes each step of the fourth embodiment of the present invention described in Table 4.
  • FIG. 5 is a series of schematic illustrations of an adsorption bed as it undergoes each step of the fifth embodiment of the present invention described in Table 5.
  • FIG. 6 is a series of schematic illustrations of an adsorption bed as it undergoes each step of the sixth embodiment of the present invention described in Table 6.
  • FIG. 7 is a series of schematic illustrations of an adsorption bed as it undergoes each step of the seventh embodiment of the present invention described in Table 7.
  • FIG. 8 is a series of schematic illustrations of an adsorption bed as it undergoes each step of the eighth embodiment of the present invention described in Table 8.
  • the present invention utilizes vacuum swing adsorption in contrast to pressure swing adsorption to recover high purity hydrogen in the range of at least 95% hydrogen, and at high recoveries in the range of 80% using a unique combination of process steps in a plurality of parallel connected adsorption beds comprising 3 to 6 parallel beds.
  • These beds are commonly manifolded, as traditional in the art, with a common feed line, a common product line and various vent, pressure equalization and purge lines.
  • the feed end of each bed is connected through appropriate manifolding with a vacuum pump.
  • a layered adsorption bed is an adsorption bed which has various distinct adsorbent layers contained within the adsorption bed in relation to the feed end and the product end. This allows discrete adsorbent selected for a particular component to remove that component prior to other components being removed by other adsorbents selected for such other components.
  • the following adsorptive gas separation cycle embodiments are suggested to recover hydrogen from a low pressure (4125 psig), low hydrogen purity ( ⁇ 60%) feed stream.
  • a key application for this process is the purification of low heating value, low hydrogen concentration refinery off gas streams containing significant levels of nitrogen, methane, carbon monoxide and carbon dioxide.
  • the steps for the first embodiment having a 6 bed, 1 equalization, feed repressurization process cycle are:
  • Table 1 depicts the time chart for this VSA embodiment.
  • the pressure equalization step in this cycle makes it most suited for the higher feed pressure part of the operating spectrum while the product assisted feed repressurization aspect of this cycle makes it most suited for the lower feed purity part of the operating spectrum.
  • the process is more energy efficient at the expense of increased capital equipment so the cycle is more suited for applications where unit power costs are high relative to capital equipment costs.
  • it is also possible to eliminate the product surge tank associated with conventional prior art designs.
  • the first bed at the top of the Table goes through the sequence of feed gas mixture repressurization, optionally using a portion of the product produced in another bed to assist repressurizing the first bed, identified as FEED REPRESS/PROD ASSIST;
  • the next step is introduction of feed gas mixture to adsorb more strongly adsorbable components while producing a product of less strongly adsorbable components, identified as FEED PRODUCT;
  • the third step is cocurrent depressurization of the first bed while the inlet of the bed is closed off to provide pressure equalization gas for the fourth bed, identified as CoC DEPRESS;
  • the fourth step occurring in the first bed is further cocurrently depressurizing the bed to provide purge gas for the fifth bed undergoing vacuum purge while at the same time countercurrently venting the first bed, identified as PROV PUR/BLOWDOWN;
  • the next step for the first bed is countercurrent evacuation under vacuum conditions by connecting the feed end of the bed to a source of vacuum such as a vacuum pump, identified as
  • FIG. 1 This sequence identified in Table 1 is illustrated with regard to FIG. 1.
  • the first of six parallel connected adsorption beds is illustrated in the eight steps sequentially identified in Table 1.
  • FIG. 1 is not a representation of eight parallel beds, but rather the same bed shown in a sequence of succeeding operations.
  • bed a 1 in the first step undergoes feed (optional product) repressurization.
  • That same bed in the next process step in the sequence depicted as a 2 undergoes introduction of feed for adsorption more strongly adsorbed components to produce a product of less strong adsorbed component or hydrogen.
  • some of the product may be transferred from the effluent end of bed a 2 to another bed which is undergoing the initial repressurization illustrated in a 1 .
  • the first bed is then shown after the end of the feed step to undergo cocurrent depressurization to provide equalization repressurization gas to another bed by connecting product end to product end or effluent end to effluent end.
  • the first bed shown in a 3 is illustrated as connecting with a bed which is at that time undergoing what eventually will be the process step of a 7 for the first bed.
  • this pressure equalization can also occur from feed end to feed end, from effluent to effluent end, or from both ends simultaneously.
  • the first bed then undergoes simultaneous cocurrent depressurization to provide purge gas while being countercurrently vented to remove waste gas or more strongly adsorbed component. This is shown with regard to a 4 .
  • the first bed in step a 4 is connected to another bed undergoing vacuum purge at this time as will occur in the first bed during the step of a 6 as illustrated.
  • the first bed is then countercurrently evacuated as illustrated in a 5 by connection to an appropriate vacuum source, such as a vacuum pump.
  • the first bed as illustrated in a 6 is subject to countercurrent vacuum purging using cocurrent depressurization gas from another bed at that point in time undergoing the prior step of the first bed, identified as a 4 .
  • the purge effluent is also removed by appropriate vacuum source, such as a vacuum pump.
  • the first bed is then initially repressurized with pressure equalization gas as illustrated in a 7 . This gas is provided from another bed undergoing what was previously illustrated for the first bed in a 3 .
  • Co-current depressurization gas is provided on a product end to product end (effluent end to effluent end) and optionally can also be provided in a feed end to feed end or in a simultaneous feed end to feed end and effluent end to effluent end basis.
  • the first bed is subject to an idle step for timing purposes as illustrated in a 8 .
  • Each bed of the six bed embodiment would undergo a similar series of steps as illustrated in FIG. 1 with the time relation of one bed to the other as illustrated in Table 1.
  • a specific application of the 6 bed product assisted feed repressurization cycle described uses a four-layer adsorption bed consisting of 3.5 feet of activated carbon followed by 2 feet of 13X zeolite followed by 1.5 feet of 5A zeolite followed by 5 feet of calcium exchanged X zeolite for the removal of large feed concentrations (>1%) of carbon monoxide and carbon dioxide down to ppm levels with only moderate thermal cycling in the sorbent bed.
  • Specific feed conditions for this application demonstration were 75 psig and 75° F. with a composition of 2% CO, 22% CO 2 , 55% N 2 and 21% H 2 .
  • the base cycle has a hydrogen recovery of 85% at 97% purity with a 0.15 mlbmol/(lb 6 min. cycle) hydrogen in product capacity and 0.83 mlbmol/(lb 6 min. cycle) feed capacity as calculated by simulation.
  • the second cycle employing 6 beds with solely product repressurization and one equalization step, is depicted in Table 2.
  • the cycle steps and sequence are identical to the 6 bed product assisted feed repressurization cycle with the exception that the repressurization step replaces the idle step and the feed steps are divided differently to provide sufficient product flow for the product repressurization step.
  • two beds are on feed and under vacuum continuously throughout the cycle. This embodiment is better than the first embodiment at relatively higher feed purities.
  • This second embodiment identified in Table 2 is also a six bed process undergoing a sequential series of ten steps. Again, the beds are represented on the vertical axis and their respective process steps are represented on the horizontal axis. With regard to the first bed, each bed will undergo a series of steps including feed gas mixture to produce product, identified as FEED>PROD; feed gas mixture introduction to produce product and repressurization gas, identified as F>P+RP; another step of feed gas mixture introduction to provide product, identified as FEED>PROD; another step of feed gas mixture introduction to provide product and repressurization gas, identified as F>P+RP; cocurrent depressurization to provide pressure equalization gas for the fourth bed, identified as CoC DEPRESS; a simultaneous cocurrent depressurization to provide purge gas and countercurrent venting wherein the purge gas is provided to the fifth bed, this step identified as PROV PUR/BLOWDOWN; a countercurrent evacuation step, identified as EVACUATION; a countercurrent vacuum purge step in which cocurrent depressurization gas
  • This process embodiment is illustrated with regard to FIG. 2.
  • This embodiment is illustrated in a comparable manner as the first embodiment with regard to FIG. 1.
  • the illustration is of only one bed showing a series of sequential steps that are performed on that bed in time sequence in relation to Table 2.
  • the drawing will be described with relation to the first bed although it is understood that each bed will perform a comparable series of steps.
  • the first bed will undergo feed gas mixture introduction to produce product as illustrated in a 21 .
  • the first bed will provide some of its product as repressurization gas as identified in a 22 .
  • the first bed will go back to dedicated product production as illustrated with regard to a 23 .
  • feed gas introduction ends with joint production of product and product for repressurization as illustrated with regard to a 24 .
  • the first bed provides product for repressurization to other beds undergoing the steps illustrated with regard to the first bed in a 30 .
  • the first bed is then cocurrently depressurized to provide pressure equalization gas as illustrated in a 25 .
  • This gas would be provided to another of the beds undergoing pressure equalization as illustrated with regard to the first bed at a 29 .
  • pressurization could be done from feed end to feed end or simultaneously from feed end to feed end and effluent end to effluent end.
  • the first bed then undergoes cocurrent depressurization to provide purge gas while simultaneously being vented countercurrently. This is illustrated with regard to the first bed at a 26 .
  • the co-current depressurization gas would be provided to another bed undergoing vacuum purge as is illustrated with regard to the first bed at a 28 .
  • the first bed is then countercurrently evacuated by connection to a vacuum source such as a vacuum pump as illustrated at a 27 .
  • the first bed then undergoes vacuum purging with cocurrent depressurization gas and connection to an appropriate vacuum source, such as a vacuum pump as illustrated with regard to the first bed at a 28 .
  • the source of the purge gas would be co-current depressurization gas from another of the beds undergoing the step illustrated with regard to the first bed at a 26 .
  • the first bed next is initially repressurized using equalization gas as illustrated with regard to a 29 using co-current depressurization gas from another bed under what is illustrated with regard to the first bed at a 25 . Again, optionally, this pressure equalization can be done also feed end to feed end or simultaneously from feed end to feed end and effluent end to effluent end. Finally, the first bed undergoes countercurrent product repressurization illustrated with regard to a 30 . All of the beds will undergo the process steps that are identified with regard to the first bed illustrated with a 21 through a 30 . However their time relationship is identified with regard to Table 2.
  • the third cycle employing 5 beds with product assisted feed repressurization and no equalization steps, is depicted in Table 3.
  • the cycle steps and sequence are identical to the 6 bed product assisted feed repressurization option with the exception that there are no pressure equalization or idle steps so only 5 beds are needed. Again, two beds are on feed and under vacuum continuously throughout the cycle while only one bed continuously provides a constant product flow. This embodiment is better than the first embodiment at relatively lower feed pressures.
  • the series of steps performed in five parallel connected beds for the third cycle is identified in Table 3 and includes feed gas mixture repressurization, identified as FEED REPRESS; product production from introduction of feed gas mixture for adsorption of the more strongly adsorbed components, identified as FEED PRODUCT; simultaneous cocurrent depressurization to provide purge gas and countercurrent vent, identified as PROV PUR/BLOWDOWN; countercurrent evacuation, identified as EVACUATION; and countercurrent vacuum purge with cocurrent depressurization gas, identified as VACUUM PURGE.
  • the arrangement is comparable to the other tables with regard to beds being identified on the vertical axis and process steps on the horizontal axis.
  • This process sequence in Table 3 is illustrated with regard to a first bed in FIG. 3.
  • the first bed at a 31 undergoes feed repressurization but could optionally simultaneously undergo countercurrent product repressurization from another of the beds undergoing what is depicted for the first bed at a 32 .
  • the first bed is then placed on product production by introduction of feed gas mixture, adsorption of more strongly adsorbed components and the production of a product of less strongly adsorbed component, as depicted at a 32 .
  • the first bed then undergoes simultaneous cocurrent depressurization to provide purge gas and countercurrent venting, as depicted at a 33 .
  • the bed then undergoes countercurrent evacuation, as depicted at a 34 , by connection to an appropriate vacuum source, such as a vacuum pump.
  • an appropriate vacuum source such as a vacuum pump.
  • the first bed undergoes countercurrent vacuum purging with cocurrent depressurization gas from another bed undergoing the step illustrated with regard to the first bed at a 33 .
  • the countercurrent vacuum purging is depicted at a 35 .
  • Connection to an appropriate vacuum source, such as a vacuum pump, is also depicted.
  • Each bed undergoes a series of steps as illustrated for the first bed comparable to the steps a 31 through a 35 . However, they are in time relationship one to another as identified in Table 3.
  • a specific application of the 5 bed product assisted feed repressurization cycle described uses a four-layer adsorption bed consisting of 3 feet of activated carbon followed by I foot of 13X zeolite followed by 2.5 feet of 5A zeolite followed by 5.5 feet of calcium exchanged X zeolite for the removal of large feed concentrations (>1%) of carbon monoxide and carbon dioxide down to ppm levels with minimal thermal cycling in the sorbent bed.
  • Specific feed conditions for this application demonstration were 10 psig and 75° F. with a composition of 22% CO, 8% CO 2 , 53% N 2 , and 17% H 2 .
  • the third cycle has hydrogen recovery of 68% at 97% purity with a 0.061 mlbmol/(lb 6 min. cycle) hydrogen in product capacity and 0.53 mlbmol/(lb 6 min. cycle) feed capacity as calculated by simulation.
  • the fourth cycle embodiment employing 5 beds with solely product repressurization and no equalization steps, is depicted in Table 4.
  • the cycle steps and sequence are identical to the 5 bed feed repressurization option with the exception that the repressurization step shifts the evacuation and vacuum purge more forward in the cycle and the feed steps are divided differently to provide sufficient product flow for the product repressurization step.
  • two beds are on feed and under vacuum continuously throughout the cycle. This embodiment is better than the third embodiment at relatively higher feed purities.
  • Table 4 demonstrates the eight process steps along the horizontal axis which are performed in five parallel connected adsorption beds along the vertical axis of the table.
  • the process steps are introduction of feed gas mixture to absorb more strongly adsorbed component and produce less strongly adsorbed component product, identified as FEED>PROD; feed gas mixture to produce product and repressurization gas, identified as F>P+RP; feed gas mixture to produce product, identified as FEED>PROD; feed gas mixture introduction to produce product and repressurization gas, identified as F>P+RP; simultaneous cocurrent depressurization to provide purge gas and countercurrent venting, identified as PROV PUR/BLOWDOWN; countercurrent evacuation, identified as EVACUATION; countercurrent vacuum purge using cocurrent depressurization gas, identified as VACUUM PURGE; and product repressurization identified as REPRESS.
  • Each bed will undergo similar process steps in varied time sequence with regard to that depicted in Table 4.
  • the process steps are illustrated with regard to FIG. 4.
  • the illustrations identify the process steps which the first bed undergoes, but it is understood that each bed will undergo a similar series of steps.
  • feed gas is introduced into the first bed to produce product.
  • feed gas is introduced to produce product and product repressurization gas which is illustrated going to another bed undergoing the step illustrated for the first bed at a 48 .
  • the first bed then undergoes the step illustrated at a 43 , comparable to a 41 , and next a step a 44 comparable to step a 42 .
  • the first bed then undergoes cocurrent depressurization to provide purge gas while undergoing simultaneous countercurrent venting as depicted at a 45 . Countercurrent evacuation is performed on the first bed as depicted at a 46 .
  • Countercurrent vacuum purge is depicted at a 47 with regard to the first bed wherein it is connected to an appropriate source of vacuum, such as a vacuum pump and receives cocurrent depressurization gas from another of the beds undergoing what is depicted for the first bed at a 45 .
  • the first bed is then countercurrent repressurized with product gas as depicted at a 48 receiving product gas from other beds undergoing the step depicted with regard to the first bed of a 42 and a 44 .
  • Each bed with regard to the time sequence illustrated in Table 4 will undergo the illustrated steps of FIG. 4 with regard to a 41 through a 48 .
  • the fifth cycle embodiment employing 4 beds with optional product assisted feed repressurization and one equalization step, is depicted in Table 5.
  • the cycle steps and sequence are identical to the 6 bed product assisted feed repressurization embodiment with the exceptions that only one bed is on feed or under vacuum at a time so only 4 beds are needed and the optional product assisted repressurization step occurs separately from the feed repressurization step.
  • This embodiment is better than the corresponding 6 bed embodiment when unit power costs are low relative to capital equipment costs (smaller plants).
  • This fifth embodiment the steps of which are identified in Table 5, is performed in four parallel connected beds represented on the vertical axis of Table 5 while the process steps which each bed undergoes are represented on the horizontal axis.
  • Those steps include: feed gas mixture repressurization, identified as FEED REPRESS; feed gas mixture introduction to adsorb more strong adsorbed components and produce a product of less strongly adsorbed components as well as producing product repressurization gas for another bed, identified as FEED PRODUCT +RP; cocurrent depressurization to provide pressure equalization gas to the third bed, identified as COC DP; simultaneous cocurrent depressurization to provide purge gas to the fourth bed while undergoing countercurrent venting identified as PROV PUR/BLOWDOWN; countercurrent evacuation identified as EVAC; countercurrent vacuum purge with cocurrent depressurization gas from the second bed, identified as VACUUM PURGE; initial repressurization with countercurrent pressure equalization gas provided from the third bed undergoing cocurrent depressurization with the option of additionally doing feed to
  • the first bed initially goes through feed gas mixture repressurization illustrated with regard to a 51 .
  • the first bed then produces product as illustrated in a 52 and produces repressurization gas for a bed undergoing the same step as depicted for the first bed at a 58 .
  • the first bed is then cocurrent depressurized to provide pressure equalization gas, as depicted in a 53 , this gas can go to another bed under the same step as illustrated for the first bed at a 57 .
  • equalization gas can also be transferred feed end to feed end of the bed or simultaneously transferred feed end to feed end and effluent end to effluent end of the bed.
  • the first bed then undergoes cocurrent depressurization to provide purge gas with the simultaneous countercurrent venting as depicted at a 54 .
  • the purge gas is transferred to another bed undergoing countercurrent purge as depicted for the first bed at a 56 .
  • the first bed is then countercurrently evacuated as depicted at a 55 .
  • the bed is connected to a source of vacuum such as vacuum pump.
  • the first bed then undergoes countercurrent vacuum purge by being connected to a source of vacuum, such as a vacuum pump, while receiving cocurrent depressurization gas from another bed undergoing the step as depicted for the first bed at a.sub. 54.
  • This vacuum purge is illustrated at a
  • the first bed then undergoes pressure equalization as depicted at a 57 with co-current depressurization gas provided from a bed undergoing the step depicted for the first bed at a 53 .
  • feed to feed pressure equalization or simultaneous feed to feed and effluent to effluent pressure equalization could be performed.
  • the first bed then undergoes product repressurization as depicted at a 58 with a portion of the product from another bed undergoing the step depicted for the first bed at a 52 .
  • product repressurization may be omitted and the first bed will undergo an idle step at a 58 .
  • Each bed undergoes the steps depicted in a through a 58 as identified in Table 5.
  • the sixth cycle embodiment employing 4 beds with solely product repressurization and one equalization step, is depicted in Table 6.
  • the cycle steps and sequence are identical to the 6 bed product only repressurization embodiment with the exception that only one bed is on feed or under vacuum at a time so only 4 beds are needed.
  • This embodiment is better than the corresponding 6 bed embodiment when unit power costs are low relative to capital equipment costs (smaller plants).
  • Table 6 shows an embodiment of the present invention using four beds with an eight step cycle sequence.
  • the four beds are depicted along the vertical axis and the cycle steps are depicted along the horizontal axis of the table.
  • Each bed goes through the sequence of steps including: feed to produce product, identified as FEED>PROD; feed to produce product and to provide repressurization gas, identified as FEED>PROD+REPRESS; cocurrent depressurization to provide pressure equalization gas for the third bed, identified as CoC DP; simultaneous cocurrent depressurization to provide purge gas along with countercurrent venting, identified as PROV PUR/BLOWDOWN; countercurrent evacuation, identified as EVAC; countercurrent vacuum purge with purge gas provided from the second bed, identified as CCC VACUUM PURGE; initial pressurization with pressure equalization gas provided by the cocurrent depressurization of the third bed, identified as P EQUAL; and product repressurization provided from the fourth bed, identified as PRODUCT REPRESS.
  • Each bed undergoes
  • FIG. 6 wherein the first bed is illustrated sequentially in each individual step experienced by all four of the beds, identified in FIG. 6 as a 61 through a 68 .
  • the first bed is depicted at a 61 as feed gas mixture is introduced and a less strongly adsorbed product is produced at the effluent end of the bed.
  • product is produced, as well as repressurization gas for another bed undergoing the same step as depicted for the first bed at a 68 .
  • Co-current depressurization to provide pressure equalization gas is accomplished in the first bed as depicted at a 63 , the equalization gas being provided to another bed undergoing the same step as is depicted for the first bed at a 67 .
  • feed to feed pressure equalization or simultaneous feed to feed and effluent to effluent pressure equalization could also be accomplished.
  • the first bed then undergoes cocurrent depressurization to provide purge gas simultaneous with countercurrent venting as depicted in a 64 .
  • the purge gas is supplied to another of the four beds presently undergoing the same step as depicted for the first bed at a 66 .
  • the first bed then undergoes countercurrent evacuation by being connected to a source of vacuum, such as a vacuum pump as depicted in a 65 .
  • the first bed is then vacuum purged countercurrently by being supplied with purge gas from another bed undergoing the same step as depicted for the first bed at a 64 .
  • the vacuum purging depicted in a 66 is accomplished by connecting the first bed to a source of vacuum such as a vacuum pump.
  • the first bed is then initially repressurized using cocurrent depressurization gas as pressure equalization gas as depicted in a 67 . This co-current depressurization gas is provided for pressure equalization from a bed currently undergoing cocurrent depressurization as depicted for the first bed at a 63 .
  • this can be a feed to feed pressure equalization or a simultaneous feed to feed and effluent to effluent pressure equalization as well as a product to product pressure equalization.
  • the first bed is repressurized countercurrently with product gas as depicted in a 68 .
  • This product repressurization gas comes from another bed that is simultaneously undergoing the step depicted for the first bed in a 62 .
  • the seventh cycle embodiment employing 3 beds with optional product assisted feed repressurization and no equalization steps, is depicted in Table 7.
  • the cycle steps and sequence are identical to the 5 bed product assisted feed repressurization embodiment with the exceptions that only one bed is on feed or under vacuum at a time so only 3 beds are needed and the optional product assisted repressurization step occurs separately from the feed repressurization step.
  • This embodiment is better than the corresponding 5 bed embodiment when unit power costs are low relative to capital equipment costs (smaller plants).
  • Table 7 illustrates a cycle sequence for three beds as represented on the vertical axis and six steps for each bed as represented in the horizontal axis of the Table. Those steps include feed gas mixture repressurization, identified as FEED REPRESS; feed gas mixture introduced to adsorb more strongly adsorbed components to produce a product of less strongly adsorbed component, identified as FEED PRODUCT; simultaneous cocurrent depressurization to provide purge gas along with countercurrent venting, identified as PROV PUR/BLOWDOWN; countercurrent evacuation, identified as EVACUATION; countercurrent vacuum purge with cocurrent depressurization gas from the second bed, identified as VAC PURGE; and product repressurization in a countercurrent mode utilizing a portion of the product from the third bed, identified as PROD REPRESS. Each bed undergoes that series of steps but in the time sequence interrelationship per Table 7.
  • FIG. 7 These steps are illustrated in FIG. 7 with regard to the first bed and illustrated as depicted in a 71 through a 76 .
  • the feed repressurization performed cocurrently is depicted in a 71 .
  • the first bed is then subjected to feed gas mixture introduction to adsorb more strongly adsorbable components and to produce a product of less strongly adsorbable components, as depicted in a 72 .
  • a portion of the product is used to product repressurize another bed undergoing what is illustrated for the first bed in a 76 .
  • the first bed is then subjected to cocurrent depressurization to provide purge gas, while simultaneously undergoing countercurrent venting, as depicted in a 73 .
  • the co-current depressurization gas for purge is supplied to another of the beds undergoing the same step, as depicted for the first bed in a 75 .
  • the first bed is then subjected to countercurrent evacuation as depicted in a 74 by connection to a source of vacuum, such as a vacuum pump.
  • the bed then undergoes countercurrent vacuum purge as depicted in a 75 by connecting to a source of vacuum, such as a vacuum pump, while receiving cocurrent depressurization gas countercurrently from another bed undergoing the same step, as depicted for the first bed in a 73 .
  • the first bed is countercurrently product repressurized as depicted in a 76 with product repressurization gas provided from another of the beds undergoing the step depicted for the first bed in a 72 .
  • product repressurization may be omitted and the first bed will undergo an idle step at a 76 .
  • Each bed undergoes the series of steps of a 71 through a 76 , but in the interrelated time sequence as identified in Table 7.
  • the eighth cycle embodiment employing 3 beds with solely product repressurization and no equalization steps, is depicted in Table 8.
  • the cycle steps and sequence are identical to the 5 bed product repressurization embodiment with the exception that only one bed is on feed or under vacuum at a time so only 3 beds are needed.
  • This embodiment is better than the corresponding 5 bed embodiment when unit power costs are low relative to capital equipment costs (smaller plants).
  • Table 8 shows an alternative embodiment for a three bed system of the present invention using six steps for each bed.
  • the steps in the table are feed gas mixture introduction to adsorb more strongly adsorbable components to produce a product of less strongly adsorbed components at the effluent end of the bed, identified as FEED>P; the feed gas mixture is then introduced into the adsorbent bed to produce product and repressurization gas, identified as FEED>PROD+REPRESS; followed by simultaneous cocurrent depressurization to provide purge gas while countercurrently venting, identified as PROV PUR/BLOWDOWN; next proceeding to a countercurrent evacuation, identified as EVACUATION; next proceeding to countercurrent vacuum purge using cocurrent depressurization gas from the second bed, identified as VAC PURGE; and ending with product repressurization using a portion of the product from the third bed identified as PRODUCT REPRESSURIZATION.
  • the first bed has feed gas mixture introduced into it co-currently to adsorb more strongly adsorbed components and produce a product of less strongly adsorbable components at the effluent end of the bed, as depicted in a.sub. 81 .
  • the first bed continues to have feed gas mixture introduced, but produces both product and product repressurization gas as depicted in a 82 , a portion of the product repressurization gas can be provided to another of the three beds presently undergoing the step depicted for the first bed at a 86 .
  • the first bed is then simultaneously co-currently depressurized to provide purge gas while undergoing countercurrent vent, as depicted in a 83 .
  • the cocurrent depressurization gas for purge is supplied to another of the three beds currently undergoing the step depicted for the first bed in a 85 .
  • the first bed then undergoes countercurrent evacuation as depicted in a 84 , while being connected to a source of vacuum, such as a vacuum pump.
  • the regeneration of the bed is continued by countercurrent vacuum purging of the first bed as depicted in a 85 wherein cocurrent depressurization purge gas from another bed undergoing what is depicted for the first bed in a 83 is conducted into the first bed depicted in a 85 while being connected to the source of vacuum, such as the vacuum pump.
  • the bed is then repressurized countercurrently with product gas as depicted in a 86 from a bed providing product repressurization gas undergoing a step comparable to that depicted for the first bed in a 82 .
  • Each bed undergoes the series of steps depicted in a 81 through a 86 .
  • the feed and vacuum pumping steps are structured so that a constant number of beds are continuously receiving feed which eliminates the need for a feed surge tank. Also, a constant number of beds are continuously connected to the vacuum train which minimizes waste gas flow variations and permits stable operation of the vacuum pumping system.
  • the combination of the countercurrent blowdown and cocurrent provide purge steps into a single dual ended step allows the feed and vacuum regeneration times to be maximized which, in turn, maximizes process efficiency.
  • a unique aspect of the present invention is the ordering of the optional pressure equalization step, the dual end blowdown/provide purge step, and the final repressurization step combined with the timing of these steps permits a constant number of beds to be continuously connected to the vacuum train while simultaneously permitting a constant number of beds to be continuously receiving feed.
  • This combination of step order and timing also permits a more efficient use of the recycle gas to provide vacuum purge, pressure equalization, and repressurization compared with previous art. Furthermore, this combination provides for the maximum cycle time to be devoted to feed and evacuation, the most efficient production and regeneration parts of a vacuum swing adsorption purification cycle, which yields a further improvement over prior art.
  • the dual end blowdown/provide purge step permits the removal of impure waste gas in the blowdown without passing it through the vacuum train and simultaneously permits a moderately pure stream of the desired component to be used as a source for the vacuum purge gas.
  • the design of options one and three permit constant product flow operation without employing the costly product surge tank routinely used in the conventional technology.

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